N-substituted-3-(substituted hydrazino)-benzenesulfonamides

ABSTRACT

Disclosed herein are N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives of the formula (I): ##STR1## wherein R 1  and CF 3 , COOH or CCl=CClCOOH, R 2  is H, Cl, C 1  -C 3  alkyl or C 1  -C 4  alkoxycarbonyl; Z is CH or N; X 1  is C 1  -C 3  alkyl, C 1  -C 3  alkoxyl or Cl; and X 2  is C 1  -C 3  alkyl or C 1  -C 3  alkoxyl, a process for the preparation thereof, and herbicidal compositions containing the N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives as active ingredients.

This is a division of Ser. No. 667,132 filed Mar. 11, 1991, now U.S. Pat. No. 5,151,114, which is a division of Ser. No. 473,768, filed Feb. 2, 1990, now U.S. Pat. No. 5,059,238.

BACKGROUND OF THE INVENTION

1) Field of the Invention

The present invention relates to N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives, a preparation process thereof, and herbicidal compositions containing the derivatives as active ingredients.

2) Description of the Related Art

Numerous compounds have heretofore been proposed as herbicides. For example, U.S. Pat. No.4,632,695, U.S. Pat. No.4,664,695 and Japanese Patent Application LaidOpen (KOKAI) No. 129276/1987 disclose a wide variety of compounds, including N-substituted-3-substituted benzenesulfonamide derivatives containing NHC(CH₃)=CHCOCH₃, NHC(CH₃)=CHCOOCH₃, NHCH₃, OCH₂ CF₃ or SCH₂ CF₃ on the 3-position and a pyrimidine ring or a 1,3,5-triazine ring on the nitrogen atom.

There have conventionally been strong demands for herbicides capable of exhibiting reliable herbicidal activity even at such low application dosages as bringing about the advantage of reducing the amount present in the environment, herbicides capable of exhibiting selectivity between crops and weeds irrespective of variations in environmental conditions, herbicides free from crop injury to the second crop in double cropping, etc. The present invention has been completed with a view toward meeting such demands.

The present inventors have found that compounds still unreported to date and having a substituted hydrazino group on the 3-position of benzenesulfonamide as opposed to the inclusion of NHC(CH₃)=CHCOCH₃, NHC(CH₃)=CH-COOCH₃ NHCH₃, OCH₂ CF₃ or SCH₂ CF₃ on the 3-position of benzenesulfonamide in the compounds disclosed in EP-A-116518 and Japanese Patent Application Laid-Open (KOKAI) No. 129276/1987 have excellent herbicidal activity, leading to the completion of the present invention.

SUMMARY OF THE INVENTION

Therefore, an object of the invention is to provide novel compounds which show excellent herbicidal activity.

Another object of the invention is to provide a process for preparing novel compounds which show excellent herbicidal activity.

A further object of the invention is to provide intermediates useful in the preparation of novel compounds which show excellent herbicidal activity.

A still further object of the invention is to provide novel herbicidal compositions which show excellent herbicidal activity.

A still further object of the invention is to provide a method for controlling monocotyledonous or dicotyledonous weeds on an agricultural or nonagricultural land.

In one aspect of the invention, there is thus provided an N-substituted-3-(substituted hydrazino)benzenesulfonamide derivative of the formula (I): ##STR2## wherein R¹ is CF₃, COOH or CCl=CClCOOH, R² is H, Cl, C₁ -C₃ alkyl or C₁ -C₄ alkoxycarbonyl; Z is CH or N; X¹ is C₁ -C₃ alkyl, C₁ -C₃ alkoxyl or Cl; and X² is C₁ -C₃ alkyl or C₁ -C₃ alkoxyl.

In another aspect of the invention, there is also provided a process for the preparation of the abovedescribed N-substituted-3-(substituted hydrazino)benzenesulfonamide derivative, which comprises reacting a 3-(substituted hydrazino)benzenesulfonamide derivative of the formula (II): ##STR3## wherein R¹ and R² have the same meanings as defined above, with a phenylcarbamate derivative of the following formula (III): ##STR4## wherein Z, X¹ and X² have the same meanings as defined above.

In a further aspect of the invention, there is also provided a 3-(substituted hydrazino)benzenesulfonamide derivative useful as an intermediate in the preparation of the above N-substituted-3-(substituted hydrazino)benzenesulfonamide, which is represented by the following formula (II): ##STR5## wherein R¹ and R² have the same meanings as defined above.

In a still further aspect of the invention, there is also provided a 3-hydrazinobenzenesulfonamide derivative useful as an intermediate in the preparation of the above 3-(substituted hydrazino)benzenesulfonamide of the formula (II), represented by the following formula (V'): ##STR6## wherein R^(2') is H, C₁ -C₃ alkyl or C₁ -C₄ alkoxycarbonyl.

In a still further aspect of the invention, there is also provided a herbicidal composition comprising as an active ingredient the N-substituted-3-(substituted hydrazino)benzenesulfonamide derivative of the formula (I).

In a still further aspect of the invention, there is also provided a method for the control of monocotyledonous or dicotyledonous weeds on an agricultural or nonagricultural land, which comprises applying to the agricultural or non-agricultural land the N-substituted-3(substituted hydrazino)benzenesulfonamide derivative of the formula (I) or a herbicidal composition comprising said derivative.

The N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives of the present invention, which are represented by the formula (I), have not been disclosed in any publications known to the inventors of the present application, exhibit reliable herbicidal activity at low application dosages and show selectivity between crops and weeds. The herbicidal compositions of the invention, which contain the above derivatives as effective ingredients, are suitable particularly for controlling before or after germination dicotyledonous and/or monocotyledonous weeds in important crops, for example, such as wheat, rice, corn, soybean, cotton, beet, potato, tomato or the like. They are also usable for the control of weeds not only on agricultural lands such as upland fields, paddy fields and orchards but also on nonagricultural lands such as athletic fields and factory sites.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Specific examples of the N-substituted-3-(substituted hydrazino)benzenesulfonamide derivative represented by the formula (I) in the invention include those shown in Table 1.

                  TABLE 1                                                          ______________________________________                                          ##STR7##                                                                      Com-                                                                           pound                                                                          No.   R.sup.1      R.sup.2   X.sup.1                                                                               X.sup.2                                                                              Z                                    ______________________________________                                         I-1   CF.sub.3     H         OCH.sub.3                                                                             OCH.sub.3                                                                            CH                                   I-2   COOH         H         OCH.sub.3                                                                             OCH.sub.3                                                                            CH                                   I-3   CF.sub.3     Cl        OCH.sub.3                                                                             OCH.sub.3                                                                            CH                                   I-4   COOH         Cl        OCH.sub.3                                                                             OCH.sub.3                                                                            CH                                   I-5   CF.sub.3     CH.sub.3  OCH.sub.3                                                                             OCH.sub.3                                                                            CH                                   I-6   COOH         CH.sub.3  OCH.sub.3                                                                             OCH.sub.3                                                                            CH                                   I-7   CF.sub.3     COOCH.sub.3                                                                              OCH.sub.3                                                                             OCH.sub.3                                                                            CH                                   I-8   COOH         COOCH.sub.3                                                                              OCH.sub.3                                                                             OCH.sub.3                                                                            CH                                   I-9   CF.sub.3     COOC.sub.2 H.sub.5                                                                       OCH.sub.3                                                                             OCH.sub.3                                                                            CH                                   I-10  COOH         COOC.sub.2 H.sub.5                                                                       OCH.sub.3                                                                             OCH.sub.3                                                                            CH                                   I-11  CF.sub.3     COOCH.sub.3                                                                              Cl     OCH.sub.3                                                                            CH                                   I-12  COOH         COOCH.sub.3                                                                              Cl     OCH.sub.3                                                                            CH                                   I-13  CF.sub.3     COOCH.sub.3                                                                              CH.sub.3                                                                              CH.sub.3                                                                             CH                                   I-14  COOH         COOCH.sub.3                                                                              CH.sub.3                                                                              CH.sub.3                                                                             CH                                   I-15  CF.sub.3     COOCH.sub.3                                                                              OCH.sub.3                                                                             CH.sub.3                                                                             CH                                   I-16  CF.sub.3     COOCH.sub.3                                                                              OCH.sub.3                                                                             CH.sub.3                                                                             N                                    I-17  COOH         COOCH.sub.3                                                                              OCH.sub.3                                                                             CH.sub.3                                                                             N                                    I-18  CClCClCOOH   Cl        OCH.sub.3                                                                             OCH.sub.3                                                                            CH                                   I-19  CClCClCOOH   COOCH.sub.3                                                                              OCH.sub.3                                                                             OCH.sub.3                                                                            CH                                   I-20  CF.sub.3     COOCH.sub.3                                                                              OCH.sub.3                                                                             OCH.sub.3                                                                            N                                    ______________________________________                                    

The N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives represented by the formula (I) can each be synthesized by reacting a 3-(substituted hydrazino)benzenesulfonamide derivative of the formula (II) and a phenylcarbamate derivative of the following formula (III) in the presence of a base and in an organic solvent in accordance with the following reaction formula: ##STR8## wherein R¹, R², Z, X¹ and X² have the same meanings as defined above.

In the above reaction, N,N-dimethylacetamide, N-methylpyrrolidone, acetonitrile or the like can be used as an organic solvent. On the other hand, diazabicyclooctane, diazabicyclononene, diazabicycloundecene or the like can be used as a base.

The reaction is conducted at a temperature in a range of from -20° C. to 100° C., preferably from 0° C. to 50° C. for a reaction period in a range of from 0.5 hour to 24 hours.

After completion of the reaction, the reaction mixture is added to an aqueous solution of dilute hydrochloric acid and the precipitate thus formed is collected by filtration. The precipitate is dried in air and then purified by a purification technique such as reprecipitation or column chromatography or by a washing technique, whereby the intended N-substituted-3-(substituted hydrazino)benzenesulfonamide derivative represented by the formula (I) can be obtained with high purity.

The 3-(substituted hydrazino)benzenesulfonamide derivative represented by the formula (II), which is a preparation intermediate and is employed as the starting material in the above reaction, can be synthesized in accordance with the following reaction formula, using as a starting material a 3-aminobenzenesulfonamide derivative represented by the following formula (IV): ##STR9## wherein R¹ and R² have the same meanings as defined above.

Synthesis of the compound represented by the formula (II) in accordance with the above-described reaction can be practiced in the following manner. The 3-hydrazinobenzenesulfonamide derivative represented by the formula (V) - which has been obtained by diazotizing the amino group of the compound represented by the formula (IV) and reducing the thus-diazotized derivative - is stirred together with trifluoroacetaldehyde ethylhemiacetal, glyoxylic acid monohydrate or mucochloric acid at 30°-120 ° C., preferably 70°-90° C. for 0.5-8 hours in acetic acid or propionic acid or at room temperature for 5-7 hours in 6 N sulfuric acid. After completion of the reaction, the reaction product is collected from the reaction mixture by filtration or the reaction mixture is evaporated to dryness under reduced pressure and if necessary, is purified by washing, whereby the compound represented by the formula (II) can be obtained with good purity.

The compound represented by the formula (IV), which was used in the above reaction formula, can be obtained from the corresponding nitrobenzene derivative, for example, by using the process described in Bull. Chem. Soc. Jpn., 55,3824 (1982); or from the corresponding 3-nitroaniline derivatives, for example, by the process described in Chem. Ber., 90, 841 (1957) or J. Macromol. Sci. Chem., 1969, 941, namely, by synthesizing 3-nitrobenzenesulfonamide derivatives and then reducing the nitro groups with SnCl₂ in methanol or ethanol containing 35% hydrochloric acid.

Further, the compound represented by the formula (III) can be obtained from phenyl chloroformate and the corresponding 2-amino-4,6-di-substituted pyrimidine (or 1,3,5-triazine), for example, by the process described in European Patent Specification No. 238,070.

Specific examples of the compound represented by the formulae (II) and useful as the above preparation intermediate are summarized in Table 2.

In addition, specific examples of the compound represented by the formula (V) are shown in Table 3.

                  TABLE 2                                                          ______________________________________                                          ##STR10##                                                                     Compound                                                                       No.          R.sup.1         R.sup.2                                           ______________________________________                                         II-1         CF.sub.3        H                                                 II-2         COOH            H                                                 II-3         CF.sub.3        Cl                                                II-4         COOH            Cl                                                II-5         CF.sub.3        CH.sub.3                                          II-6         COOH            CH.sub.3                                          II-7         CF.sub.3        COOCH.sub.3                                       II-8         COOH            COOCH.sub.3                                       II-9         CF.sub.3        COOC.sub.2 H.sub.5                                II-10        COOH            COOC.sub.2 H.sub.5                                II-11        HOOCCClCCl      Cl                                                II-12        HOOCCClCCl      COOCH.sub.3                                       ______________________________________                                    

                  TABLE 3                                                          ______________________________________                                          ##STR11##                                                                     Compound                                                                       No.                  R.sup.2                                                   ______________________________________                                         V-1                  H                                                         V-2                  Cl                                                        V-3                  CH.sub.3                                                  V-4                  COOCH.sub.3                                               V-5                  COOC.sub.2 H.sub.5                                        ______________________________________                                    

The N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives exhibit reliable herbicidal activity at low application dosages and show selectivity between crops and weeds. The herbicidal compositions of the invention, which contain the above compounds as effective ingredients, are therefore suitable for controlling either before or after emergence monocotyledonous weeds and/or dicotyledonous weeds in important crops such as wheat, rice, corn, soybean, cotton, beet, potato and tomato.

Exemplary dicotyledonous weeds which can be controlled by the herbicides of the invention include Amaranthus, Bidens, Stellaria, Solanum, Ahutilon, Convolvulus, Matricaria, Galium, Lindernia, etc.

Illustrative monocotyledonous weeds include Echinochloa, Setaria, Digitaria, Avena, Cyperus, Alisma, Monochoria, etc.

The herbicidal compositions of the invention may take any preparation forms such as wettable powder, emulsion, powder, granule and the like. Known agronomicallyacceptable vehicles (diluents) and aids can be used.

The applicable places of the herbicides according to the invention range from agricultural lands such as upland fields, paddy fields and orchard to non-agricultural lands such as athletic fields and factory sites.

EXAMPLES

The present invention will hereinafter be described by the following examples.

SYNTHESIS EXAMPLE 1

Synthesis of methyl 2-[(4,6-dimethoxypyrimidin-2yl)aminocarbonylaminosulfonyl]-4-[(2,2,2-trifluoroethylidene)hydrazino]benzoate (Compound No. I-7)

At room temperature, 166 mg (0.5 mmol) of methyl 2-(aminosulfonyl)-4-[(2,2,2-trifluoroethlidene)hydrazino]benzoate and 137.5 mg (0.5 mmol) of phenyl (4,6-dimethoxypyrimidin-2-yl)carbamate were dissolved in 1.5 ml of N,N-dimethylacetamide. Then, 86.1 mg of 1,8-diazabicyclo[5.4.0]undec-7-ene were added, followed by stirring for 5 minutes. The resultant mixture was allowed to stand for 15 hours. Thereafter, 0.2 ml of 35% hydrochloric acid was added to 20 ml of ice water, followed by the addition of the reaction mixture in 0.2 ml portions under stirring. After the reaction mixture was stirred for 20 minutes, the resulting precipitate was collected by filtration and dried in air. Using dichloromethane as an eluent, the crude product was purified by chromatography on a column of silica gel ("WAKO GEL C-300", trade name; product of Wako Pure Chemical Industries, Ltd.). The title compound was obtained as a white solid. Yield: 162 mg (64%). Melting point: 201°-202° C. Its physicochemical properties are shown in Table 4.

SYNTHESIS EXAMPLE 2 Synthesis of methyl 2-[(4,6-dimethoxy-1,3,5-triazin2-yl)aminocarbonylaminosulfonyl]-4-[(2,2,2-trifluoroethylidene)hydrazino]benzoate (Compound No. I-20)

At room temperature, 166 mg (0.5 mmol) of methyl 2-(aminosulfonyl)-4-[(2,2,2-trifluoroethlidene)hydrazino]benzoate and 138 mg (0.5 mmol) of phenyl (4,6-dimethoxy1,3,5-triazin-2-yl)carbamate were dissolved in 1.5 ml of N,N-dimethylacetamide. Then, 86.1 mg of 1,8-diazabicyclo[5.4.0]undec-7-ene were added, followed by stirring for 5 minutes. The resultant mixture was allowed to stand for 6 hours. Thereafter, 0.2 ml of 35% hydrochloric acid was added to 30 ml of ice water, followed by the addition of the reaction mixture in 0.2 ml portions under stirring. After the reaction mixture was stirred for 20 minutes, the resulting precipitate was collected by filtration and dried in air. Using as an eluent a 1:9 mixed solvent of methyl acetate and benzene, the crude product was purified by chromatography on a column of silica gel ("WAKO GEL C-300", trade name; product of Wako Pure Chemical Industries, Ltd.). The title compound was obtained as a white solid. Yield: 103 mg (41%). Melting point: 117°-119° C. (foamed). Its physicochemical properties are shown in Table 4.

The other N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives shown in Table 1 were also synthesized in a similar manner to Synthesis Example 1. Namely, after obtaining crude products by a similar procedure to Synthesis Example 1, they were separately purified by chromatography on a silica gel column or washing. Physicochemical properties of each of the N-substituted-3(substituted hydrazino)benzenesulfonamide derivatives are shown in Table 4. Incidentally, in Table 4 and in Tables 5 and 6 which will be given subsequently, the abbreviations in the columns for NMR data have the following meanings:

δ: (ppm), s: singlet, d: doublet, t: triplet,

q: quartet, m: multiplet, dd: double doublet,

br: broad.

Further, with respect to the individual N-substituted-3-(substituted hydrazino)benzenesulfonamide derivatives, the solvents employed upon purification thereof and the yields attained were as follows:

    ______________________________________                                         Compound No.                                                                               Solvent employed Yield (%)                                         ______________________________________                                         Compounds purified by column chromatography:                                   I-1         CH.sub.2 Cl.sub.2                                                                               49                                                I-7         CH.sub.2 Cl.sub.2                                                                               64                                                I-9         CH.sub.2 Cl.sub.2                                                                               59                                                I-11        CH.sub.2 Cl.sub.2                                                                               64                                                I-13        Methyl acetate + benzene                                                                        67                                                I-14        Methyl acetate + benzene                                                                        55                                                I-15        Methyl acetate + benzene                                                                        24                                                I-20        Methyl acetate + benzene                                                                        41                                                Compounds purified by washing:                                                 I-2         CH.sub.2 Cl.sub.2                                                                               68                                                I-3         petroleum ether  93                                                I-4         CH.sub.2 Cl.sub.2 + petroleum ether                                                             79                                                I-5         petroleum ether  81                                                I-6         petroleum ether  62                                                I-8         CH.sub.2 Cl.sub.2 + petroleum ether                                                             70                                                I-10        CH.sub.2 Cl.sub.2                                                                               50                                                I-12        CH.sub.2 Cl.sub.2 + hexane                                                                      80                                                I-14        CH.sub.2 Cl.sub.2 + hexane                                                                      70                                                I-17        CH.sub.2 Cl.sub.2 + petroleum ether                                                             57                                                I-18        CH.sub.2 Cl.sub.2                                                                               55                                                I-19        CH.sub.2 Cl.sub.2                                                                               30                                                ______________________________________                                    

                                      TABLE 4                                      __________________________________________________________________________                Melting                                                             Com-       Point or                                                            pound                                                                              MS (m/e)                                                                              Decomposition                                                       No. (A)*.sup.)                                                                        (B)**.sup.)                                                                        Point (°C.)                                                                     IR (KBr, cm.sup.-1)                                                                     NMR (δ)                                      __________________________________________________________________________     I-1 293                                                                               155 132-135 3300-2700, 1710,                                                                        CDCl.sub.3                                                                           3.947(6H, s) 5.783(1H, s) 7.068(1H, q,                                         4.27Hz) 7.443-7.738                                     Decomposition                                                                          1610, 1570, 1490,                                                                             (5H, m) 8.536(1H, s) 12.701(1H, s)                              1450, 1370, 1250,                                                              1160, 1120, 580                                             I-2 -- 155 168-170 3350-2500, 1710,                                                                        d.sub.6 -DMSO                                                                        3.908(6H, s) 5.990(1H, s) 7.179(1H, s)                                         7.374(1H, dd,                                           Decomposition                                                                          1600, 1570, 1490,                                                                             6.71Hz, 1.83Hz) 7.482-7.533(2H, m)                                             7.707(1H, s) 10.548(1H, s)                                      1450, 1360, 1310,                                                                             11.468(1H, s) 12.594br(2H, s)                                   1220, 1200, 1160,                                                              580                                                         I-3 327                                                                               155 204-206 3420-2800, 1710,                                                                        d.sub.6 -DMSO                                                                        3.898(6H, s) 5.990(1H, s) 7.29(1H, d,                                          7.3Hz) 7.430(1H, q,                                             1600, 1570, 1490,                                                                             4.2Hz) 7.59(1H, dd, 7.3Hz, 1.4Hz)                                              7.797(1H, d, 1.4Hz) 10.65br                                     1440, 1370, 1350,                                                                             (1H, s) 11.525(1H, s) 13.019(1H, s)                             1280, 1250, 1220                                            I-4 -- 155 146-147 3300-2600, 1700,                                                                        d.sub.6 -DMSO                                                                        3.915(6H, s) 6.020(1H, s) 7.196(1H, s)                                         7.372(1H, dd, 8.55Hz,                                   Decomposition                                                                          1610, 1570, 1490,                                                                             2.44Hz) 7.580(1H, d, 8.55Hz) 7.878(1H,                                         d, 2.44Hz) 10.665br                                             1450, 1360, 1290,                                                                             (1H, s) 11.559(1H, s) 12.994br(1H, s)                                          13.011br(1H, s)                                                 1220, 1200, 1160,                                                              1030, 820, 630, 580                                         I-5 307                                                                               155 187-189 3300-2600, 3280,                                                                        CDCl.sub.3                                                                           2.585(3H, s) 3.954(6H, s) 5.805(1H, s)                                         6.980(1H, q, 4.3Hz)                                     Decomposition                                                                          2930, 1710, 1600,                                                                             7.221(1H, d, 8.5Hz) 7.306(1H, s)                                               7.394(1H, dd, 8.5Hz, 1.5Hz)                                     1570, 1490, 1450,                                                                             7.719(1H, d, 1.5Hz) 8.414(1H, s)                                               12.735(1H, s)                                                   1360, 1240, 1160,                                                              1120, 760, 700, 590                                         I-6 -- 155 149-152 3250, 3150-2600,                                                                        d.sub.6 -DMSO                                                                        2.504(3H, s) 3.911(6H, s) 6.020(1H, s)                                         7.155(1H, s) 7.289-7.370                                Decomposition                                                                          1710, 1610, 1570,                                                                             (2H, m) 7.782(1H, s) 10.587(1H, s)                                             11.417(1H, s) 12.508br                                          1490, 1450, 1370,                                                                             (1H, s) 12.728br(1H, s)                                         1360, 1220, 1190,                                                              1170, 590                                                   I-7 351                                                                               155 201-202 3400-2800, 3260,                                                                        d.sub.6 -DMSO                                                                        3.762(3H, s) 3.947(6H, s) 6.010(1H, s)                                         7.366(1H, d, 8Hz)                                               3100, 2950, 1720,                                                                             7.494(1H, q, 4.9Hz) 7.765(1H, d, 8Hz)                                          7.855(1H, s) 10.631                                             1600, 1580, 1490,                                                                             (1H, s) 11.771(1H, s) 12.579(1H, s)                             1450, 1370, 1350,                                                              1300, 1270, 1240,                                                              1190, 1170, 1110,                                                              890, 820, 630, 580                                          I-8 -- 155 148-149 3400-2700, 1710,                                                                        d.sub.6 -DMSO                                                                        3.795(3H, s) 3.950(6H, s) 6.010(1H, s)                                         7.257(1H, s)                                            Decomposition                                                                          1600, 1570, 1440,                                                                             7.440(1H, dd, 8.55Hz, 1.83Hz) 7.777(1H,                                        d, 8.55Hz) 7.903(1H,                                            1370, 1350, 1270,                                                                             d, 1.83Hz) 10.638(1H, s) 11.783(1H, s)                                         12.574(1H, s) 12.750br                                          1230, 1210, 1190,                                                                             (1H, s)                                                         1160, 1110, 580                                             I-9 365                                                                               155 125-128 3320-2700, 3280,                                                                        CDCl.sub.3                                                                           1.347(3H, t, 7.33Hz) 4.010(6H, s)                                              4.296(2H, q, 7.33Hz) 5.790                              Decomposition                                                                          1710, 1590, 1570,                                                                             (1H, s) 7.107(1H, q, 4.27Hz) 7.457(1H,                                         s) 7.491(1H, dd, 8.54                                           1490, 1440, 1350,                                                                             Hz, 2.44Hz) 7.780(1H, d, 8.54Hz)                                               7.865(1H, d, 2.44Hz)                                            1290, 1260, 1230,                                                                             9.024(1H, s) 12.662(1H,s)                                       1190, 1160, 1110,                                                              630, 580                                                    I-10                                                                               -- 155 138-140 3300-2600, 1710,                                                                        d.sub.6 -DMSO                                                                        1.237(3H, t, 7.33Hz) 3.945(6H, s)                                              4.222(2H, q, 7.33Hz) 6.003                              Decomposition                                                                          1600, 1570, 1490,                                                                             (1H, s) 7.250(1H, s) 7.431(1H, dd,                                             8.55Hz) 7.770(1H, d, 8.55                                       1450, 1360, 1270,                                                                             Hz) 7.900(1H, d, 1.83Hz) 10.634(1H, s)                                         11.759(1H, s) 12.555                                            1240, 1220, 1200,                                                                             (1H, s) 12.750br(1H, s)                                         1170, 580                                                   I-11                                                                               351                                                                               159 144-146 3340, 1740, 1610,                                                                       CDCl.sub.3                                                                           3.881(3H, s) 4.147(3H, s) 6.495(1H, s)                                         7.169(1H, q, 3.66Hz)                                    Decomposed                                                                             1580, 1470, 1375,                                                                             7.528(1H, dd, 8.55Hz, 2.44Hz) 7.805(1H,                                        d, 8.55Hz) 7.872(1H,                                            1310, 1290, 1190,                                                                             d, 2.44Hz) 7.894(1H, s) 8.966(1H, s)                                           12.198(1H, s)                                                   1130, 590                                                   I-12                                                                               -- 159 140-143 3400-2800, 1730,                                                                        d.sub.6 -DMSO                                                                        3.788(3H, s) 4.045(3H, s) 6.879(1H, s)                                         7.250(1H, s)                                            Decomposed                                                                             1590, 1580, 1450,                                                                             7.442(1H, dd, 8.55Hz, 2.44Hz) 7.792(1H,                                        d, 8.55Hz) 7.897(1H,                                            1360, 1295, 1275,                                                                             d, 2.44Hz) 10.902(1H, s) 11.771(1H, s)                                         11.951br(1H, s)                                                 1125, 590      12.750br(1H, s)                              I-13                                                                               351                                                                               123 154-158 3300-2700, 1730,                                                                        CDCl.sub.3                                                                           2.514(6H, s) 3.878(3H, s) 6.759(1H, s)                                         7.190(1H, q, 3.06Hz)                                    Decomposed                                                                             1720, 1620, 1480,                                                                             7.521(1H, dd, 8.54Hz, 2.44Hz) 7.765(1H,                                        d, 8.54Hz) 7.889(1H,                                            1470, 1450, 1360,                                                                             d, 2.44Hz) 8.275(1H, s) 9.269(1H, s)                                           13.370(1H, s)                                                   1310, 1290, 1260,                                                              1130, 600                                                   I-14                                                                               -- 123 145-150 3400-2600, 1750br,                                                                      d.sub.6 -DMSO                                                                        2.435(6H, s) 3.757(3H, s) 7.016(1H, s)                                         7.245(1H, s)                                            Decomposed                                                                             1635, 1590, 1490,                                                                             7.430(1H, dd, 7.94Hz, 1.83Hz) 7.764(1H,                                        d, 7.94Hz) 7.886(1H,                                            1480, 1460, 1370,                                                                             d, 1.83Hz) 10.602(1H, s) 11.761(1H, s)                                         12.750br(1H, s) 13.304                                          1300, 1270, 1190,                                                                             (1H, s)                                                         1150, 610                                                   I-15                                                                               351                                                                               139 152-154 3300-2800, 1750,                                                                        CDCl.sub.3                                                                           2.492(3H, s) 3.866(3H, s) 3.986(3H, s)                                         6.295(1H, s) 7.158(1H, q,                               Decomposed                                                                             1620, 1590, 1470,                                                                             3.05Hz) 7.509(1H, dd, 8.54Hz, 2.44Hz)                                          7.775(1H, d, 8.54Hz)                                            1450, 1370, 1310,                                                                             7.792(1H, s) 7.884(1H, d, 2.44Hz)                                              9.227(1H, s) 13.275(1H, s)                                      1280, 1260, 1130,                                                              600                                                         I-16                                                                               351                                                                               140 101-105 3300-2800, 1730,                                                                        CDCl.sub.3                                                                           2.633(3H, s) 3.898(3H, s) 4.086(3H, s)                                         7.194(1H, q, 3.66Hz)                                    Decomposed                                                                             1610, 1570, 1450,                                                                             7.526(1H, dd, 8.55Hz, 2.44Hz) 7.804(1H,                                        d, 8.55Hz) 7.842(1H,                                            1360, 1300, 1270,                                                                             d, 2.44Hz) 8.235(1H, s) 9.154(1H, s)                                           12.615(1H, s)                                                   1240, 1170, 1110,                                                              820, 590                                                    I-17                                                                               -- 140 144-146 3350-2700, 1760,                                                                        d.sub.6 -DMSO                                                                        2.500(3H, s) 3.803(3H, s) 3.996(3H, s)                                         7.250(1H, s)                                            Decomposed                                                                             1630, 1600, 1480,                                                                             7.453(1H, dd, 8.54Hz, 2.44Hz) 7.799(1H,                                        d, 8.54Hz) 7.891(1H,                                            1390, 1310, 1280,                                                                             d, 2.44Hz) 11.085(1H, s) 11.776(1H, s)                                         12.513(1H, s) 12.75                                             1200, 1180, 1150,                                                                             (1H, s)                                                         850, 620                                                    I-18                                                                               -- 155 142-144 3300-2700, 1720,                                                                        d.sub.6 -DMSO                                                                        3.915(6H, s) 6.025(1H, s) 7.321(1H, dd,                                        8.54Hz, 2.44Hz)                                         Decomposed                                                                             1600, 1580, 1540,                                                                             7.563(1H, d, 8.54Hz) 7.831(1H, d,                                              2.44Hz) 8.795(1H, s) 10.697                                     1500, 1450, 1360,                                                                             (1H, s) 11.666(1H, s) 13.02br(1H, s) H                                         of COOH was not                                                 1260, 1220, 1170,                                                                             observed.                                                       1020, 810, 760,                                                                690, 590                                                    I-19                                                                               -- 155 148-149 3300-2800, 1730,                                                                        d.sub.6 -DMSO                                                                        3.752(3H, s) 3.947(6H, s) 6.012(1H, s)                                         7.370(1H, d, 8.55Hz)                                    Decomposed                                                                             1610, 1580, 1450,                                                                             7.764(1H, d, 8.55Hz) 7.875(1H, s)                                              8.830(1H, s) 10.634(1H, s)                                      1380, 1290, 1270,                                                                             11.898(1H, s) 12.577(1H, s) H of COOH                                          was not observed.                                               1250, 1220, 1170,                                                              1110, 1020, 590                                             I-20                                                                               351                                                                               156 117-119 3300, 3200-2800,                                                                        CDCl.sub.3                                                                           3.898(3H, s) 4.110(6H, s) 7.167(1H, q,                                         3.66Hz)                                                 Decomposed                                                                             1730, 1600, 1570,                                                                             7.527(1H, dd, 8.55Hz, 1.33Hz) 7.799(1H,                                        d, 8.55Hz) 7.845(1H,                                            1500, 1460, 1380,                                                                             d, 1.83Hz) 8.111(1H, s) 8.959(1H, s)                                           12.261(1H, s)                                                   1360, 1300, 1270,                                                              1245, 1170, 1120,                                                              815, 590                                                    __________________________________________________________________________      ##STR12##                                                                      -                                                                              ##STR13##                                                                

SYNTHESIS EXAMPLE 3 Synthesis of preparation intermediate, methyl 2-(aminosulfonyl)-4-[(2,2,2-trifluoroethylidene)hydrazino]benzoate (Comoound No. II-7)

(1) Synthesis of methyl 2-(aminosulfonyl)-4-hydrazinobenzoate (Compound No. V-4):

To a mixture of 6 ml of 35% hydrochloric acid and 6 ml of water, 3 g of methyl 4-amino-2-(aminosulfonyl)benzoate were added, followed by stirring at room temperature for 5 minutes. The reaction mixture was then cooled with ice water, followed by the addition of 3 ml of an aqueous solution of 0.95 g of sodium nitrite under stirring over 2 minutes to conduct diazotization.

In 6.52 ml of 35% hydrochloric acid, 6.78 g of stannous chloride were dissolved. The resulting solution was cooled with ice water and stirred, followed by the addition of the diazotized compound prepared above.

After the resultant mixture was stirred for 20 minutes, it was left over for 15 hours in a refrigerator. The reaction mixture was then transferred into a 3-l beaker, to which 38 g of sodium bicarbonate were then added under stirring to adjust the pH to 6. The mixture thus prepared was then extracted twice with 300 ml of methyl acetate. The extract was dried over sodium sulfate, and methyl acetate was distilled off to obtain a pale yellow solid. Yield: 2.76 g (86%). Melting point: 168°-170° C. Its physicochemical properties are shown in Table 6.

(2) Synthesis of methyl 2-(aminosulfonyl)-4-[(2,2,2-trifluoroethylidene)hydrazino]benzoate (Compound No. II-7):

In 4 ml of acetic acid, 367.5 mg (1.5 mmol) of the compound synthesized in the above procedure (1) (Compound No. V-4) and 0.21 ml of trifluoroacetaldehyde ethylhemiacetal were dissolved, followed by stirring at 80° C. for 3 hours. Acetic acid was then distilled off from the reaction mixture and 30 ml of ice water were added to the pale yellow residue. The insoluble matter was collected by filtration and then dried in air. The title compound was obtained as a pale yellow solid. Yield: 421 mg (86%). Its physicochemical properties are shown in Table 5.

The other compounds shown in Table 2 were also synthesized in accordance with the above reaction formula. Either the following reaction conditions (a) or (b) were employed.

(a) After reaction for 3-5 hours at 80°-90° C. in acetic acid in a flask, acetic acid was distilled off, and the reaction product was scraped out from the flask. As an alternative, the reaction product was washed out with a poor solvent from the flask, collected by filtration and then dried in air.

(b) After reaction for 5-7 hours at room temperature in 6 N sulfuric acid, the insoluble matter was collected by filtration, washed with water and then dried in air [see Chem. Ber., 115, 3706-18 (1982)].

The following yields were achieved under the respective reaction conditions:

    ______________________________________                                         Compound No.                                                                               Reaction conditions                                                                             Yield (%)                                         ______________________________________                                         II-1        (a) (scraped out)                                                                               98                                                II-2        (b)              93                                                II-3        (b)              76                                                II-4        (b)              96                                                II-5        (b)              40                                                II-6        (b)              85                                                II-7        (a) water        86                                                II-8        (a) H.sub.2 O/methanol (1/1)                                                                    46                                                II-9        (a) H.sub.2 O/ethanol (1/1)                                                                     58                                                 II-10      (a) H.sub.2 O/acetonitrile (1/1)                                                                27                                                 II-11      (b)              75                                                 II-12      (a) H.sub.2 O, CH.sub.2 Cl.sub.2                                                                32                                                ______________________________________                                    

The physicochemical properties of these compounds are shown in Table 5.

In addition, the physicochemical properties of the other compounds shown in preparation intermediates in Table 3 are given in Table 6.

                                      TABLE 5                                      __________________________________________________________________________                 Melting                                                                        Point or De-                                                       Compound    composition                                                        No.   MS (m/e)                                                                             Point (°C.)                                                                    IR (KBr, cm.sup.-1)                                                                              NMR (δ)                             __________________________________________________________________________     II-1  267   150-155                                                                               3410, 3270, 1590, 1490, 1420, 1340,                               (M.sup.+)    1300, 1280, 1240, 1170, 1120, 1100,                                            900, 870, 780, 730, 680, 600, 590                           II-2  199   188-190                                                                               3300, 3200, 3250-2700, 1690, 1600,                                (M.sup.+  -44)                                                                       Decomposed                                                                            1560, 1470, 1370, 1320, 1260, 1210,                                            1160, 980, 890, 800, 740, 680, 590, 520                     II-3  301   164-167                                                                               3410, 3280, 1600, 1470, 1400, 1340,                               (M.sup.+)    1300, 1290, 1270, 1250, 1170, 1140,                                            1110, 880, 830, 600                                         II-4  233   195-197                                                                               3340, 3260, 3160, 3080, 3300-2700,                                (M.sup.+  -44)                                                                       Decomposed                                                                            1690, 1600, 1560, 1460, 1380, 1370,                                            1340, 1310, 1260, 1230, 1160,                                                  830, 770, 590                                               II-5  281   168-169                                                                               3310, 3230, 1625, 1610, 1520, 1490,                                                              d.sub.6 -DMSO:2,500(3H, s) 7.109(1H,                                           dd, 8.5Hz, 1.8Hz)                               (M.sup.+ )                                                                           Decomposed                                                                            1410, 1350, 1290, 1250, 1160, 1140,                                                              7.270(1H, d, 8.5Hz) 7.341(1H, q,                                               4.88Hz) 7.377(2H, s)                                         1120, 1070, 900, 830,780, 700, 610, 510                                                          7.614(1H, d, 1.8Hz) 11.263(1H, s)         II-6        172-173                                                                               3370, 3250, 3100-2300, 1670, 1550,                                                               d.sub.6 -DMSO:2.507(3H, s) 7.138(1H,                                           s) 7.183(1H, dd,                                      Decomposed                                                                            1490, 1440, 1320, 1290, 1240, 1180,                                                              8.54 Hz, 2.44Hz) 7.272(1H, d,                                                  8.54Hz) 7.367(2H, s)                                         1150, 1140, 870, 600                                                                             7.657(1H, d, 2.44Hz) 11.324(1H, s)                                             H of COOH was not observed.               II-7  325   227-230                                                                               3350, 3280, 3250, 2950, 1700, 1690,                               (M.sup.+)                                                                            Decomposed                                                                            1600, 1540, 1440, 1330, 1300, 1280,                                            1260, 1170, 1150, 1110, 870, 780,                                              760, 590                                                    II-8  257   197-200                                                                               3300-2800br, 3250, 3150, 3080, 1710,                                                             d.sub.6 -DMSO:3823(3H, s) 7.216(2H,                                            s) 7.238(1H, s)                                 (M.sup.+  -44)                                                                       Decomposed                                                                            1690, 1600, 1560, 1320, 1300, 1270,                                                              7.299(1H, dd, 7.93Hz, 1.83Hz)                                                  7.737(1H, d, 7.93Hz)                                         1240, 1160, 1120, 850,830, 780,590                                                               7.743(1H, d, 1.83Hz) 11.666(1H, s)                                             12.645br(1H, s)                           II-9  339   238-241                                                                               3350, 3280, 3250, 1680, 1600, 1330,                               (M.sup.+)                                                                            Decomposed                                                                            1300, 1280, 1240, 1170, 1150, 1110,                                            880, 780, 700, 600                                           II-10                                                                               271   138-140                                                                               3300-2700, 3250, 1710, 1690, 1600,                                (M.sup.+  -44)                                                                       Decomposed                                                                            1560, 1320, 1270, 1240, 1160, 1120,                                            820, 780                                                     II-11                                                                               353   224-226                                                                               3400, 3280, 3200-2700, 1670, 1610,                                                               d.sub.6 -DMSO:7.216(1H, dd, 8.55Hz,                                            2.44 Hz)                                        (M.sup.+  -18)                                                                       Decomposed                                                                            1510, 1460, 1340, 1270, 1170, 1020,                                                              7.497(1H, d, 8.55Hz) 7.575(2H, s)                                              7.731(1H, d, 2.44Hz)                                                           8.764(1H, s) 11.612(1H, s)                                                     H of COOH was not observed.                II-12                                                                               377   239-241                                                                               3380, 3260, 3200-2700, 1710, 1685,                                                               d.sub.6 -DMSO:3.823(3H, s)                                                     7.223-7.760(5H, m) 8.822(1H, s)                 (M.sup.+  -18)                                                                       Decomposed                                                                            1610, 1550, 1530, 1520, 1330, 1290,                                                              11.832(1H, s) H of COOH was not                                                observed.                                                    1270, 1250, 1170, 1160, 1120, 1020,                                            745, 700                                                    __________________________________________________________________________

                                      TABLE 6                                      __________________________________________________________________________               Melting                                                                        Point or De-                                                         Compound                                                                             MS  composition                                                          No.   (m/e)                                                                              Point (°C.)                                                                    IR (KBr, cm.sup.-1)                                                                           NMR (δ)                                  __________________________________________________________________________     V-I   187 113-116                                                                               3360,3350, 3300, 3220, 1500,                                                   1470, 1340, 1330, 1290, 1140,                                                  1090, 780, 680, 580, 510                                      V-2   221 155-158                                                                               3370, 3330, 3130, 2970, 1590,                                           Decomposed                                                                            1560, 1460, 1330,1270, 1160,                                                   970, 830, 740, 690, 590,                                                       550, 510                                                      V-3   201 161-164                                                                               3300, 3250, 3010, 1610, 1490,                                                                 d.sub.6 -DMSO:2.409(3H, s)                                      1300, 1160, 1140, 920, 820,                                                                   4.025br(2H, s) 6.840                                            690, 600, 520  (1H, dd, 8.5Hz, 1.8Hz)                                                         6.901(1H, s) 7.048(1H,                                                         d, 8.5Hz) 7.148(2H, s)                                                         7.349(1H, d, 1.8Hz)                            V-4   245 168-170                                                                               3350, 3310, 3250, 1680, 1630,                                                  1590, 1440, 1350, 1330, 1300,                                                  1270, 1170, 1160, 780, 700, 600                               V-5   259 122-124                                                                               3320, 3270, 2980, 1700, 1590,                                           Decomposed                                                                            1370, 1320, 1300, 1270, 1250,                                                  1150, 1120, 770, 740, 700                                     __________________________________________________________________________

Compounds available in a similar manner to Synthesis Example 2 are summarized in Table 7.

                  TABLE 7                                                          ______________________________________                                          ##STR14##                                                                     Com-                                                                           pound                                                                          No.   R.sup.1      R.sup.2   X.sup.1                                                                               X.sup.2                                                                              Z                                    ______________________________________                                         I-21  CF.sub.3     H         CH.sub.3                                                                              OCH.sub.3                                                                            N                                    I-22  CF.sub.3     H         OCH.sub.3                                                                             OCH.sub.3                                                                            N                                    I-23  CF.sub.3     Cl        CH.sub.3                                                                              OCH.sub.3                                                                            N                                    I-24  CF.sub.3     Cl        OCH.sub.3                                                                             OCH.sub.3                                                                            N                                    I-25  CF.sub.3     CH.sub.3  CH.sub.3                                                                              OCH.sub.3                                                                            N                                    I-26  CF.sub.3     CH.sub.3  OCH.sub.3                                                                             OCH.sub.3                                                                            N                                    I-27  CF.sub.3     COOC.sub.2 H.sub.5                                                                       CH.sub.3                                                                              OCH.sub.3                                                                            N                                    I-28  CF.sub.3     COOC.sub.2 H.sub.5                                                                       OCH.sub.3                                                                             OCH.sub.3                                                                            N                                    I-29  COOH         H         OCH.sub.3                                                                             OCH.sub.3                                                                            N                                    I-30  COOH         Cl        OCH.sub.3                                                                             OCH.sub.3                                                                            N                                    I-31  COOH         CH.sub.3  CH.sub.3                                                                              OCH.sub.3                                                                            N                                    I-32  COOH         COOCH.sub. 3                                                                             OCH.sub.3                                                                             OCH.sub.3                                                                            N                                    I-33  COOH         COOC.sub.2 H.sub.5                                                                       CH.sub.3                                                                              OCH.sub.3                                                                            N                                    I-34  COOH         COOC.sub.2 H.sub.5                                                                       OCH.sub.3                                                                             OCH.sub.3                                                                            N                                    I-35  CClCClCOOH   H         OCH.sub.3                                                                             OCH.sub.3                                                                            N                                    I-36  CClCClCOOH   Cl        CH.sub.3                                                                              OCH.sub.3                                                                            N                                    I-37  CClCClCOOH   CH.sub.3  OCH.sub.3                                                                             OCH.sub.3                                                                            N                                    I-38  CClCClCOOH   COOCH.sub.3                                                                              CH.sub.3                                                                              OCH.sub.3                                                                            N                                    I-39  CClCClCOOH   COOCH.sub.3                                                                              OCH.sub.3                                                                             OCH.sub.3                                                                            N                                    I-40  CClCClCOOH   COOC.sub.2 H.sub.5                                                                       OCH.sub.3                                                                             OCH.sub.3                                                                            N                                    ______________________________________                                    

Formulation examples and tests will hereinafter be described. It should be borne in mind that the vehicles (diluents) and aids, their mixing ratios and effective components can vary in wide ranges, respectively.

FORMULATION EXAMPLE 1 Wettable

    ______________________________________                                         Compound (Compound No. I-7)                                                                         50 parts                                                  A salt of ligninsulfonic acid                                                                        5 parts                                                  A salt of alkylsulfonic acid                                                                         3 parts                                                  Diatomaceous earth   42 parts                                                  ______________________________________                                    

The above ingredients are mixed and ground into a wettable powder. For application, it is diluted with water.

FORMULATION EXAMPLE 2 Emulsion

    ______________________________________                                         Compound (Compound No. I-11)                                                                        25 parts                                                  Xylene               65 parts                                                  Polyoxyethylene alkylaryl ether                                                                     10 parts                                                  ______________________________________                                    

The above ingredients are mixed intimately into an emulsion. For application, it is diluted with water.

FORMULATION EXAMPLE 3 Granule

    ______________________________________                                         Compound (Compound No. I-17)                                                                         8 parts                                                  Bentonite            40 parts                                                  Clay                 45 parts                                                  A salt of ligninsulfonic acid                                                                        7 parts                                                  ______________________________________                                    

The above ingredients are mixed intimately and after the addition of water, were kneaded and then formed into granules by an extruding granulator. They were then dried to provide a granular formulation, namely, a granule.

Test 1: Test on Herbicidal Activity by Foliar Application

Herbicidal solutions of each test compound, which had been prepared by dissolving at predetermined concentrations such a wettable powder of the test compound as that described in the above formulation example, and sprayed at dosages of 10 g/ha and 100 g/ha over foliar parts of Amaranthus retroflexus (Redroot pigweed), Bidens pilosa (Common blackjack), Sinapis arvensis (Wild mustard), Stellaria media (Common chickweed), Cassia obtusifolia (Sicklepod), Solanum nigrum (Black nightshade), Abutilon theophrasti (Velvetleaf), Convolvulus arvensis (Field bindweed), Matricaria chamomilla (Wlld chamomile), Setaria viridis (Green foxtail), Echinochloa frumentaceum (Barnyard grass), Avena farua(Wild oat), and Digitaria adscendens (Henry crabgrass) which had been allowed to grow individually to 2-4 leaf stage in pots. Fourteen days later after spraying of the test compound, its herbicidal activity was evaluated in accordance with the below-described system. The results are summarized in Table 8.

Ranking system:

Herbicidal activity

0: No effects

1: less than 31% of total kill

2: 31-50% of total kill

3: 51-70% of total kill

4: 71-90% of total kill

5: 91-100% of total kill

                                      TABLE 8                                      __________________________________________________________________________           application                                                              Compound                                                                             dosage                                                                   No.   (g/ha)                                                                               A.r.                                                                              B.p.                                                                              S.a.                                                                              S.m.                                                                              C.o.                                                                              S.n.                                                                              A.t.                                                                              C.a.                                                                              M.c.                                                                              S.v.                                                                              E.f.                                                                              A.f.                                                                              D.a.                           __________________________________________________________________________     I-1    10   5  4  5  5  1  0  3  0  2  0  0  0  0                                    100   5  5  5  5  5  1  5  1  5  1  2  5  1                              I-2    10   5  4  5  5  2  0  5  1  5  2  0  0  0                                    100   5  5  5  5  5  4  5  5  5  4  4  0  0                              I-3    10   5  5  5  5  5  3  5  4  5  0  4  0  3                                    100   5  5  5  5  5  4  5  5  5  4  5  3  3                              I-4    10   5  5  5  5  5  1  5  1  5  0  0  2  0                                    100   5  5  5  5  5  5  5  5  5  5  5  5  3                              I-5    10   5  5  5  5  5  4  5  0  5  0  2  0  0                                    100   5  5  5  5  5  5  5  3  5  2  5  0  2                              I-6    10   5  5  5  5  5  5  5  5  5  5  3  2  2                                    100   5  5  5  5  5  5  5  5  5  5  4  3  3                              I-7    10   5  5  5  5  5  5  5  4  5  5  5  3  0                                    100   5  5  5  5  5  5  5  5  5  5  5  5  5                              I-8    10   5  5  5  5  5  5  5  5  5  5  5  5  0                                    100   5  5  5  5  5  5  5  5  5  5  5  5  5                              I-9    10   5  5  5  5  5  5  5  5  5  2  2  4  0                                    100   5  5  5  5  5  5  5  5  5  5  5  5  4                              I-10   10   5  5  5  5  5  5  5  5  5  3  4  4  0                                    100   5  5  5  5  5  5  5  5  5  5  5  5  3                              I-11   10   5  5  5  5  5  5  5  3  5  4  5  0  0                                    100   5  5  5  5  5  5  5  5  5  5  5  5  2                              I-12   10   5  5  5  5  5  5  5  5  5  5  4  0  0                                    100   5  5  5  5  5  5  5  5  5  5  5  5  3                              I-13   10   5  5  5  5  5  5  5  5  5  5  5  5  0                                    100   5  5  5  5  5  5  5  5  5  5  5  5  5                              I-14   10   5  5  5  5  5  5  5  5  5  5  5  5  5                                    100   5  5  5  5  5  5  5  5  5  5  5  5  5                              I-15   10   5  5  5  5  5  5  5  5  5  5  4  5  1                                    100   5  5  5  5  5  5  5  5  5  5  5  5  5                              I-16   10   5  5  5  5  5  5  5  5  5  4  2  2  0                                    100   5  5  5  5  5  5  5  5  5  5  5  5  3                              I-17   10   5  5  5  5  5  5  5  5  5  5  1  2  0                                    100   5  5  5  5  5  5  5  5  5  5  5  5  5                              I-18   10   5  5  5  5  3  3  5  5  5  2  0  0  0                                    100   5  5  5  5  5  5  5  5  5  4  4  4  0                              I-19   10   5  5  5  5  4  4  5  5  5  3  1  1  0                                    100   5  5  5  5  5  5  5  5  5  4  4  4  1                              I-20   10   5  5  5  5  5  5  5  5  5  4  2  2  0                                    100   5  5  5  5  5  5  5  5  5  5  5  5  4                              __________________________________________________________________________     Note)                                                                          A.r.: Amaranthus retroflexus                                                                 S.n.: Solanum nigrum                                                                         S.v.: Setaria viridis                              B.p.: Bidens pilosa                                                                          A.t.: Abutilon theophrasti                                                                   E.f.: Echinochloa frumentaceum                     S.a.: Sinapis arvensis                                                                       C.a.: Convolvulus arvensis                                                                   A.f.: Avena fatua                                  S.m.: Stellaria media                                                                        M.c.: Matricaria chamomilla                                                                  D.a.: Digitaria adscendens                         C.o.: Cassia obtusifolia                                                  

Test 2: Germination Test of Seeds

Two sheets of filter paper were placed in a superposed relation in each of Petri dishes having a diameter of 9 cm. Water suspensions of each test compound (concentrations of the active ingredient: 1 ppm and 50 ppm) were separately poured in an amount of 5 ml per dish into the Petri dishes. Seeds of Amaranthus retroflexus (Redroot pigweed), Bidens pilosa (Common blackjack), Matricaria chamomilla (Wild chamomile), Solanum nigrum (Black nightshade), Echinochloa oryzicola (Barnyard grass), Cyperus iria (Rice flatsedge) and Setaria viridis (Green foxtail) were placed at a rate of 10 seeds per dish in the Petri dishes. They were thereafter allowed to germinate in a constant-temperature chamber at 28° C. Fourteen days later after placement in the Petri dishes, the degrees of germination and growth inhibition were observed visually. The observation results were ranked in accordance with the below-described 6-stage system. The results are summarized in Table 9.

Growth inhibition rate

0: No inhibition

1: less than 31%

2: 31-50%

3: 51-70%

4: 71-90%

5: 91-100%

                  TABLE 9                                                          ______________________________________                                         Com-   Concen-                                                                 pound  tration                                                                 No.    (ppm)    A.r.   B.p. M.c. S.n. E.o. C.i. S.v.                           ______________________________________                                         I-1     1       3      3    4    1    4    3    2                                     50       5      4    4    5    4    4    4                              I-2     1       3      0    3    3    0    3    1                                     50       4      4    4    4    3    4    5                              I-3     1       3      3    4    2    4    3    4                                     50       4      3    4    5    5    4    5                              I-4     1       4      3    4    3    4    3    3                                     50       4      4    4    5    5    4    5                              I-5     1       2      0    2    2    2    3    2                                     50       3      3    3    3    5    4    5                              I-6     1       3      2    3    2    3    2    3                                     50       5      4    3    4    4    3    4                              I-7     1       3      3    4    3    4    5    5                                     50       3      4    4    5    5    5    5                              I-8     1       4      3    5    3    5    5    5                                     50       4      4    5    3    5    5    5                              I-9     1       4      4    5    4    4    4    3                                     50       5      4    5    4    5    5    5                              I-10    1       3      3    5    4    1    4    4                                     50       4      4    5    4    4    4    5                              I-11    1       2      1    1    5    1    2    1                                     50       4      4    3    5    3    4    4                              I-12    1       2      0    4    1    1    3    1                                     50       3      2    4    5    2    4    3                              I-13    1       3      2    4    1    2    2    2                                     50       4      4    4    5    4    4    4                              I-14    1       2      1    1    1    1    1    1                                     50       3      3    4    4    3    4    4                              I-15    1       3      2    3    2    1    4    3                                     50       4      4    5    3    4    4    4                              I-16    1       1      0    3    2    0    2    1                                     50       3      3    4    4    4    4    5                              I-17    1       1      1    2    2    0    2    0                                     50       2      2    3    4    1    4    3                              I-18    1       3      2    3    3    4    4    4                                     50       4      3    5    3    5    4    5                              I-19    1       3      2    4    2    3    3    4                                     50       4      3    4    4    5    4    4                              I-20    1       1      1    3    2    0    2    1                                     50       3      3    4    4    3    4    4                              ______________________________________                                         Note)                                                                          A.r.: Amaranthus retroflexus                                                                   E.o.: Echinochloa oryzicola                                    B.p.: Bidens pilosa                                                                            C.i.: Cyperus iria                                             M.c.: Matricaria chamomilla                                                                    S.v.: Setaria viridis                                          S.n.: Solanum nigrum                                                       

We claim:
 1. A 3-(substituted hydrazino)benzenesulfonamide derivative of the following formula: ##STR15## wherein R¹ is CF₃, COOH or CCl=CClCOOH and R² is H, Cl, C₁ -C₃ alkyl or C₁ -C₄ alkoxycarbonyl.
 2. A 3-hydrazinobenzenesulfonamide derivative of the following formula: ##STR16## wherein R^(2'), is H, C₁ -C₃ alkyl or C₁ -C₄ alkoxycarbonyl. 